Pietersen and Smith have waged a bitter war of words in recent years after the England player decided to switch allegiance in protest at the quota system employed in South Africa to promote black talent.
The 26-year-old has been a thorn in the Proteas' side ever since scoring 454 runs in seven matches against them in an away one-day series in 2005.
"We'll look to knock him over early," said Smith.
"We have plans for him as we have for everyone else. We've got to be well prepared and we will be well prepared.
"He is one of the best one-day players at the moment. He's a vital cog in their setup and we have respect for his cricketing ability."
South Africa will be in a must-win situation on Tuesday, having secured just six points from as many matches. Defending champions Australia, New Zealand and Sri Lanka have already qualified for the semi-finals.
A win for England will almost certainly put them into the last four.
When asked of the chokers' tag ahead of the pressure game, Smith said: "If we win tomorrow we can put a lot of things behind us. But winning tomorrow is not winning the World Cup.
"It will be a good start and take us into the semi-finals. Maybe, we have not adapted at certain times. You need a little bit of luck also at certain phases in the game. We have not played to our potential yet."
The South African captain said his team were capable of raising their game in the crunch match.
"We haven't played the cricket we know we are capable of. We have not achieved our levels which has been disappointing, but we know if we perform to our levels, we can can turn it all around.
"There are just three games left and if you win three you win the World Cup. It's a massive game, the one we are concentrating on.
"It's a big game for both the teams and there will be a lot of heat and pressure on both the sides. I'm pretty sure it will be a very explosive game."
Smith said his team needed to seize the early initiatve on a Kensington Oval track having pace and bounce.
"It's going to be one of those World Cups where a lot depends on adapting to the conditions and that's the issue up front. England have played here before, but this is our first game here," Smith said.
"Adaptability will be the key. The pace and bounce will suit us, but we've got to find our feet early."
Smith conceded his side had not played to their potential in the previous games which saw them lose to Bangladesh and New Zealand.
"Everyone will like to have a perfect run-up to the World Cup, but I don't think they come around too often. It's certainly a challenge for us, a challenge for both the teams.
"It's important to concentrate on cricket and if we play good cricket it will give us an opportunity to go into the semi-finals. That's what we are focusing on and the key is to get our selection right."
Like South Africa, Michael Vaughan's Englishmen are also seeking a victory in this game to sustain their chances of advancing to the semi-finals. They have four points and need to win against South Africa and the West Indies.